WO2013127515A1 - Procédé de fabrication d'un produit en acier - Google Patents

Procédé de fabrication d'un produit en acier Download PDF

Info

Publication number
WO2013127515A1
WO2013127515A1 PCT/EP2013/000549 EP2013000549W WO2013127515A1 WO 2013127515 A1 WO2013127515 A1 WO 2013127515A1 EP 2013000549 W EP2013000549 W EP 2013000549W WO 2013127515 A1 WO2013127515 A1 WO 2013127515A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel substrate
solution
slag material
slag
steel
Prior art date
Application number
PCT/EP2013/000549
Other languages
English (en)
Inventor
Fouzia Hannour
Jose Reyes Flores Ramirez
Uazir Orion Bezerra DE OLIVEIRA
Original Assignee
Tata Steel Nederland Technology B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tata Steel Nederland Technology B.V. filed Critical Tata Steel Nederland Technology B.V.
Priority to EP13706177.6A priority Critical patent/EP2820162A1/fr
Publication of WO2013127515A1 publication Critical patent/WO2013127515A1/fr
Priority to HK15106471.8A priority patent/HK1206074A1/xx

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/72—Temporary coatings or embedding materials applied before or during heat treatment during chemical change of surfaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0294—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a localised treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/43—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also hexavalent chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings

Definitions

  • the present invention relates to a method for manufacturing a steel product and the product thus produced.
  • Steel making slag includes blast furnace slag, blast oxygen furnace slag and electric arc furnace slag types.
  • Blast furnace (BF) slag is produced as a by-product during the manufacture of pig iron.
  • BF slag may be recycled externally, for instance as an aggregate in cements or as a fertiliser in agriculture, BF slag is often not re-used by the steel manufacturer. In this respect BF slag may not be re-introduced into the sinter plant or into the blast furnace without further treatment due to the presence of phosphorous, which forms phosphate precipitates that are detrimental to the steel thus produced.
  • Blast oxygen furnace slag is produced as a by-product of the basic oxygen steel (BOS) making process in which molten pig iron from a blast furnace is charged into a basic oxygen furnace (BOF) together with scrap metal, fluxes, alloys and high purity oxygen.
  • Oxygen is used primarily for the decarburisation and conversion of molten pig iron to liquid steel, while alloys are added to tailor the properties of the steel itself.
  • Fluxes such as burnt lime or dolomite are used to form slag, the purpose of which is to absorb impurities in the steel and those introduced during the steel making process.
  • BOF slag The chemical composition and physical properties of BOF slag prevents or at least limits steel manufacturers from recycling BOF slag themselves.
  • the presence of phosphorous in BOF slag also prevents it from being re-introduced into the steel making process.
  • BOF slag has the further disadvantage in that it contains Cr(lll) (Cr 2 0 3 ) compounds, that if subjected to a high temperature treatment, for instance in a cement kiln (approximately 1400°C), oxidise to form hexavalent chromium toxic compounds that are hazardous to human health.
  • BOF slag The relatively high CaO content in BOF slag relative to BF and EAF slag also makes BOF slag less preferred as material for use in the manufacture of concrete. This is primarily due to the increased risk of cracks forming in the concrete caused by the hydration reaction of CaO to calcium hydroxide ((CaOH 2 ). Electric arc furnace slag is also a by-product of the steel making process.
  • the composition, properties and applications of EAF slag are broadly similar to those of BOF slag, although EAF slag generally has a lower content of free magnesium and calcium oxides. It is an object of the present invention to find a new use for steel making slag.
  • a method for manufacturing a steel product which comprises the steps of:
  • steel substrates preferably carbon steel substrates
  • a corrosion protective layer is formed on the steel substrate surface from one or more oxides of the slag material. This corrosion protective layer acts both as a barrier layer and as a passivation layer, which protects the steel against abrasion and prevents or at least reduces corrosive electrolytes from contacting the steel substrate surface respectively.
  • Steel substrates contacted with the solution comprising the slag material are less susceptible to corrosion relative to steel substrates contacted with a solution in which the slag material is absent.
  • the slag material comprises blast furnace slag, blast oxygen furnace slag and electric arc furnace slag. All of these slag materials contain calcium oxide (CaO) which increases the pH of the solution comprising the slag material. By increasing the pH, the rate of corrosion is reduced.
  • the solution comprising the slag material is aqueous. This has the advantage that the aqueous solution can be used instead of or in addition to aqueous solutions such as water that are used to cool and/or clean steel substrates in current steel manufacturing processes.
  • the solution comprising the slag material has a pH of at least 6, preferably between 7.5 and 12.5.
  • the pH behaviour of acidic, neutral and alkaline solutions were studied both before and after a slag material (1 %) was added to the respective solutions.
  • a slag material 1 % was added to the respective solutions.
  • pH neutral solutions pH neutral solutions were obtained, whereas the addition of the slag material to a pH neutral solution caused the pH of the solution to change from pH neutral to alkaline (pH >12.5).
  • the slag material was added to an alkaline solution, the solution remained alkaline.
  • the best corrosion protective properties were obtained when the steel substrate was contacted with a solution having an alkaline pH. This has been attributed, at least in part, to the reduced H + concentration at alkaline pH, which limits the corrosive cathodic half reaction for hydrogen reduction.
  • the composition of the corrosion protective layer was influenced by the pH of the solution containing the slag material.
  • the corrosion protective layer consisted mainly of a compound comprising Ca, Si, Mg and O as main components.
  • the compound comprised elements selected from the group consisting of Si, Al, P, S, Ca, V, Mg, O and Fe.
  • the difference in the composition of the corrosion protective layer has been attributed to the solubility of the oxides in acidic and alkaline pH solutions.
  • the above corrosion protective layers were formed on uncoated cold-rolled steel substrates.
  • the slag material comprises 20 to 75 wt% CaO.
  • the CaO content is within the aforementioned range very good corrosion protection is obtained.
  • the improved corrosion protection has been attributed to CaO increasing the pH of the solution and contributing to the formation of a passivation layer that prevents or at least reduces corrosive electrolytes from contacting the steel surface.
  • the corrosion protective properties of the BOF slag are further improved when the above oxides were present in the above concentrations. This has been attributed to the elements of the above oxides interacting to form a passivation layer, while CaO and to a lesser extent alumina, contribute to increasing and then maintaining the pH of the solution.
  • oxides of Mn, Mg, Ti, P, Fe, V, Na and Cr can all serve as passivation layers and/or as corrosion inhibitors thereby inhibiting corrosion of the underlying steel substrate.
  • the steel substrate is contacted with the solution comprising the slag material after the steel substrate has been subjected to a milling operation, preferably the milling operation comprises hot-roll milling, cold roll milling, plate milling, bar milling and rod milling.
  • the solution comprising the slag material is contacted with the milled steel substrate, the substrate having a temperature of at least 100°C, preferably between 700 and 1100 ° C.
  • the substrate having a temperature of at least 100°C, preferably between 700 and 1100 ° C.
  • the steel substrate is a coiled strip that is immersed in the solution comprising the slag material.
  • This is particularly advantageous for hot-roll milled steel strip substrates.
  • the cooling of hot-rolled coils in a cooling bath is typical within the steel manufacturing industry, especially for coils produced via the direct sheet plant (DSP) process.
  • These coils typically exhibit a temperature of at least 700°C before entering the cooling bath.
  • the milled steel substrate is pickled and thereafter contacted with the solution comprising the slag material.
  • Steel substrates such as strip and wire are pickled to remove oxides (scale) that are formed at the steel substrate surface during milling e.g. hot-roll milling.
  • a typical pickling line comprises a scale breaker, a pickling bath containing solutions of hydrochloric acid or sulphuric acid, and a rinsing section in which the pickled steel is rinsed with water to remove traces of pickling products, pickle residues and contaminants from the steel substrate surface.
  • the pickling operation occurs before the strip substrate is coiled.
  • the use of the solution comprising the slag material to rinse the pickled steel substrate in place of water results in the formation of a passivation layer on the surface of the steel substrate, which prevents or at least reduces the reoccurrence of oxide scale forming at the steel substrate surface.
  • the solution comprising the slag material is typically alkaline, when the solution is contacted with an acidic solution originating from the pickling bath, for instance on the surface of the pickled steel substrate, a further advantage is realised in that the pickling solution is neutralised.
  • the steel substrate is cold-roll milled to form a cold rolled strip, which strip is thereafter contacted with the solution comprising the slag material. It is preferred that the strip is contacted with the solution following a temper mill operation of the cold-roll mill. Preferably the solution is applied by spraying or by dipping the temper-milled substrate prior to the step of coiling.
  • a temporary corrosion protection layer is formed on the surface of the steel substrate, which provides corrosion protection during storage and/or transport of the steel substrates.
  • Particularly preferred cold-rolled steel substrates comprise high strength steels, advanced high strength steels and ultra high strength steels.
  • the steel substrate is hot-roll milled and then cold-roll milled.
  • the steel substrate may be contacted with the solution comprising the slag material and afforded additional corrosion protection.
  • the steel substrate is provided with a zinc or zinc alloy coating and contacted with the solution comprising the slag material.
  • the zinc alloy comprises Zn as the main constituent, i.e. the alloy comprises more than 50% zinc, and one or more of Mg, Al, Si, Mn, Cu, Fe and Cr.
  • Zinc alloys selected from the group consisting of Zn-Mg, Zn- n, Zn-Fe, Zn-AI, Zn-Cu, Zn-Cr, Zn-Mg-AI and Zn-Mg-AI-Si are particularly preferred.
  • the zinc or zinc alloy coating can be applied by electro-galvanising, galvannealing or by physical vapour deposition (PVD). Hot-dip galvanising is particularly preferred since the heat from the hot-dip galvanised steel substrate can be used to remove the aqueous solvent from the BOFS solution, thereby leaving behind a corrosion protective layer of BOF slag material on the zinc or zinc alloy coating.
  • a steel substrate manufactured according to any one of the methods of the first aspect of the invention.
  • the advantages associated with the embodiments of the first aspect of the invention similarly apply to the embodiments of the second aspect of the invention.
  • the corrosion protective layer has a dry film thickness of up to 10 ⁇ , preferably between 1 and 5 ⁇ . It is preferred not to exceed a layer thickness of 10 ⁇ since the corrosion protection layer is susceptible to delaminate from the surface.
  • the corrosion protective layer is crystalline and comprises Ca and Si as main components.
  • Such a corrosion protective layer is formed when a zinc or zinc alloy coated steel is immersed in an aqueous BOF solution having an alkaline pH.
  • the corrosion protective layer is amorphous and comprises Zn and Si as main components.
  • Such a corrosion protective layer is formed when a zinc or zinc alloy coated steel is immersed in an aqueous BOF solution having a neutral pH e.g. pH 6.
  • the corrosion protective layer is amorphous and comprises Al, Si, Fe as main components.
  • Such a corrosion protective layer is formed when a zinc or zinc alloy coated steel is immersed in an aqueous BOF solution having an acidic pH.
  • FIG. 1 shows the corrosion protective layer (1 ) that has formed on the surface of a steel substrate (2) provided with a zinc coating (3).
  • BOF slag (BOFS) materials were obtained from one blast oxygen furnace and subsequently analysed using wavelength dispersive X-ray fluorescence (WDXRF) to determine their chemical composition (Table 1). Oxide (wt%)
  • Table 1 Chemical composition of BOF slag materials in wt% given by WDXRF analysis. Immersion corrosion test
  • a 1% BOF slag solution was prepared by mixing the slag material 1 (BOFS 1) having an average particle size range of (10 - 100 ⁇ ) in aqueous solution.
  • BOFS 1 slag material 1
  • steel substrates 2 and 3 are hot dip-galvanised steel substrates provided with Zn and Zn-Mg coatings respectively, each coating having a thickness of 10 ⁇
  • steel substrate 4 is a galvannealed (zinc) steel substrate having a coating thickness of 10 ⁇ .
  • Table 2 summarises the experimental conditions that were employed during the corrosion test and the results thus obtained.
  • Improved corrosion protection is afforded to both uncoated and coated steel substrates when the substrates are immersed in solutions containing BOF slag material, irrespective of whether the starting solution, i.e. the solution before the BOF slag material is provided, is acidic, pH neutral, or alkaline.
  • the improved corrosion protection is believed to be due to the formation of a corrosion protective passivation layer at the steel substrate surface and a reduction in the concentration of H + ions in the aqueous solution at increased pH, particularly alkaline pH,
  • the passivation layer acts a physical barrier to corrosive electrolytes preventing them from contacting the steel, whereas the reduced concentration of H + ions inhibits the corrosive cathodic half reaction for hydrogen reduction.
  • the substrates comprising the corrosion protective layer thereon, were first rinsed with de-ionised water and then air dried. These substrates were then characterized using the back-scattered electron mode of the SEM to differentiate metallic phases. In order to determine the elemental chemical composition of the corrosion protective layer, the substrates were coated with a thin layer of graphite to ensure a sufficient conductivity was obtained during SEM-EDS analysis. EDX data was obtained using a standard acceleration voltage of 15KeV at a working distance of 9.5mm. The results of the selective deposition experiments are shown in Table 3 below.
  • a zinc coated steel substrate was degreased and rinsed to remove any lubricant.
  • the zinc coated steel was then deposited in an aqueous solution (i.e. deionized water) containing 10% BOF slag.
  • the pH of the aqueous solution was set to pH 12 using NaOH.
  • the zinc coated steel substrate was completely immersed in the alkaline aqueous solution for 10hrs. Due to the preset pH and the existing surface charges of the substrate, calcium ions were preferentially deposited on the zinc layer forming a crystalline structure rich in zinc and calcium.
  • the alloyed layer can have thicknesses ranging from 1 to 15 pm. An immersion time of 10hrs resulted in a corrosion protection layer having a thickness of approximately 5 ⁇ .
  • a zinc coated steel is degreased and rinsed to remove any lubricant.
  • the zinc coated steel was then deposited in an aqueous solution (i.e. deionized water) containing 10% BOF slag.
  • an aqueous solution i.e. deionized water
  • the pH of the aqueous solution was adjusted to pH 2 using hydrochloric acid, sulfuric acid or nitric acid, hydrochloric acid being preferred.
  • the zinc coated steel substrate was completely immersed in the acidified aqueous solution for 10hrs.
  • aluminium, silicon, and iron ions were preferentially deposited on the zinc layer forming an amorphous structure rich in aluminium, silicon and iron and with a minor portion of calcium, vanadium and magnesium (less than 1% of the total composition).
  • the amorphous layer had a thickness between 1 and 12 pm.
  • An immersion time of 12hrs resulted in a corrosion protection layer having a thickness of approximately 6 pm.
  • the zinc coated steel was degreased and rinsed to remove any lubricant. Then, the steel was deposited in an aqueous solution (i.e. deionized water) containing is 10% BOF slag. In order to obtain the desired composition, the pH of the aqueous solution was kept neutral (pH 6). Thereafter, the zinc coated steel substrate was completely immersed in the aqueous solution for 10hrs. Due to the preset pH and the existing surface charges of the substrate, silicon ions were preferentially deposited on the zinc layer forming an amorphous structure rich in silicon and zinc with minor portions of titanium oxide, vanadium oxide and calcium (less than 1 % of the total composition). The zinc coated substrates were kept fully immersed for 24 hrs.
  • aqueous solution i.e. deionized water
  • the pH of the aqueous solution was kept neutral (pH 6).
  • the zinc coated steel substrate was completely immersed in the aqueous solution for 10hrs. Due to the preset pH and the existing surface charges of
  • an amorphous layer with a thickness of 3 microns had formed on the surface of the substrate.
  • the process can be accelerated by adding 2% sodium chloride to the solution.
  • the chloride ions act as catalyst to accelerate surface reactions, which results in silicon ions being deposited at much faster rate. In this particular case, a minor amount of chloride ions were incorporated into the deposited corrosion protection layer.
  • composition of the corrosion protective layer that is formed can be controlled by adjusting the initial pH of the aqueous solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Procédé de fabrication d'un produit en acier comprenant les étapes suivantes : (i) fournir un substrat en acier ; (ii) fournir une solution comprenant un matériau de scories ; (iii) mettre en contact le substrat en acier avec la solution comprenant le matériau de scories formant une couche de protection contre la corrosion sur la surface du substrat en acier, la couche de protection contre la corrosion étant constituée principalement d'un composé formé à partir d'oxydes compris dans le matériau de scories.
PCT/EP2013/000549 2012-02-27 2013-02-26 Procédé de fabrication d'un produit en acier WO2013127515A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13706177.6A EP2820162A1 (fr) 2012-02-27 2013-02-26 Procédé de fabrication d'un produit en acier
HK15106471.8A HK1206074A1 (en) 2012-02-27 2015-07-07 Method for manufacturing a steel product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12001274.5 2012-02-27
EP12001274 2012-02-27

Publications (1)

Publication Number Publication Date
WO2013127515A1 true WO2013127515A1 (fr) 2013-09-06

Family

ID=47750614

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/000549 WO2013127515A1 (fr) 2012-02-27 2013-02-26 Procédé de fabrication d'un produit en acier

Country Status (3)

Country Link
EP (1) EP2820162A1 (fr)
HK (1) HK1206074A1 (fr)
WO (1) WO2013127515A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107299306A (zh) * 2017-07-20 2017-10-27 首钢集团有限公司 一种中锰钢热浸镀的方法
CN109175384A (zh) * 2018-08-01 2019-01-11 四川大学 一种片状微米级铁硅铝粉的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2150777A (en) * 1934-06-09 1939-03-14 Gen Electric Alkaline coating for sheet steel
US3615903A (en) * 1968-10-03 1971-10-26 Armco Steel Corp High-purity ferrous material and method of making it
EP0045207A1 (fr) * 1980-07-30 1982-02-03 Moldline Limited Procédé pour protéger l'acier au cours du traitement thermique
JPH10251744A (ja) * 1997-03-13 1998-09-22 Kawasaki Steel Corp 連続鋳造鋳片の加熱方法
WO2003048403A1 (fr) * 2001-12-04 2003-06-12 Centre De Recherches Metallurgiques Asbl - Centrum Voor Research In De Metallurgie Vzw Procede de revetement de surface metallique
US20070141246A1 (en) * 2003-12-17 2007-06-21 Sebastien Le Craz Method for coating a metal surface with an ultrafine layer
US20080233295A1 (en) * 2007-01-31 2008-09-25 Institute Of Process Engineering, Chinese Academy Of Sciences Antioxidation coating for steel and antioxidation method using the same
EP2003216A1 (fr) * 2006-03-31 2008-12-17 Sumitomo Metal Industries Limited Procede de production de tube sans soudure en acier inoxydable biphasique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5877523A (ja) * 1981-10-31 1983-05-10 Sumitomo Metal Ind Ltd 鋼片加熱における酸化防止方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2150777A (en) * 1934-06-09 1939-03-14 Gen Electric Alkaline coating for sheet steel
US3615903A (en) * 1968-10-03 1971-10-26 Armco Steel Corp High-purity ferrous material and method of making it
EP0045207A1 (fr) * 1980-07-30 1982-02-03 Moldline Limited Procédé pour protéger l'acier au cours du traitement thermique
JPH10251744A (ja) * 1997-03-13 1998-09-22 Kawasaki Steel Corp 連続鋳造鋳片の加熱方法
WO2003048403A1 (fr) * 2001-12-04 2003-06-12 Centre De Recherches Metallurgiques Asbl - Centrum Voor Research In De Metallurgie Vzw Procede de revetement de surface metallique
US20070141246A1 (en) * 2003-12-17 2007-06-21 Sebastien Le Craz Method for coating a metal surface with an ultrafine layer
EP2003216A1 (fr) * 2006-03-31 2008-12-17 Sumitomo Metal Industries Limited Procede de production de tube sans soudure en acier inoxydable biphasique
US20080233295A1 (en) * 2007-01-31 2008-09-25 Institute Of Process Engineering, Chinese Academy Of Sciences Antioxidation coating for steel and antioxidation method using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107299306A (zh) * 2017-07-20 2017-10-27 首钢集团有限公司 一种中锰钢热浸镀的方法
CN109175384A (zh) * 2018-08-01 2019-01-11 四川大学 一种片状微米级铁硅铝粉的制备方法

Also Published As

Publication number Publication date
HK1206074A1 (en) 2015-12-31
EP2820162A1 (fr) 2015-01-07

Similar Documents

Publication Publication Date Title
CN107406988B (zh) 热浸镀锌系钢板
CA2712557C (fr) Procede pour appliquer une couche de protection metallique sur un produit plat en acier lamine a chaud ou a froid contenant 6 - 30% en poids de mn
US10584407B2 (en) Zinc alloy plated steel material having excellent weldability and processed-part corrosion resistance and method of manufacturing same
CA2373997C (fr) Procede et solution destines a mettre en oeuvre un revetement de conversion sur une surface metallique ii
JP6683258B2 (ja) 溶融Ａｌ系めっき鋼板及び溶融Ａｌ系めっき鋼板の製造方法
KR101415349B1 (ko) 절단 단부면 내식성 및 가공부 내식성이 우수한 용융 알루미늄 합금 도금 강재와 그 제조 방법
WO2007136115A1 (fr) TÔle d'acier ÉlectromagnÉtique directionnel comportant un film de revÊtement isolant de tension ÉlevÉe, et procÉdÉ de traitement du film de revÊtement isolant
TW201610235A (zh) 冷軋鋼板、冷軋鋼板的製造方法、汽車零件以及冷軋鋼板的製造設備
EP2820162A1 (fr) Procédé de fabrication d'un produit en acier
JPWO2021095442A1 (ja) めっき鋼材
JP5505053B2 (ja) 有機複合Ｍｇ系めっき鋼板
JP5114850B2 (ja) 冷延鋼板およびその製造方法
WO2014009004A1 (fr) Bande, tôle ou flan d'acier thermoformable revêtu(e), et procédé de fabrication de celle/celui-ci
US20230145863A1 (en) Method for producing hardened steel components with a conditioned zinc anti-corrosive layer
JP7453583B2 (ja) Ａｌめっきホットスタンプ鋼材
JP2002004017A (ja) 表面性状に優れた溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼材とその製造方法
JP7395749B2 (ja) 耐黄変性及びリン酸塩処理性が向上した鋼板及びその製造方法
US11795526B2 (en) Surface-treated steel sheet
CN115279944B (zh) 制备具有锌合金防腐蚀层的硬化钢组件的方法
JP3205292B2 (ja) 耐食性およびめっき密着性に優れた溶融亜鉛めっき鋼板の製造方法
WO2012139769A1 (fr) Feuillard, tôle ou ébauche apte au formage à chaud, son procédé de production, procédé de formage à chaud d'un produit et produit formé à chaud
KR20140097466A (ko) 아연 또는 아연­합금 코팅된 기판을 위한 건식­정위치 내식성 코팅
JPH10237668A (ja) 耐白錆性に優れたクロメート処理極低鉛溶融亜鉛めっき鋼板の製造方法
WO2019169199A1 (fr) Revêtement d'alliage à base de zinc pour acier et procédés
CN115279945A (zh) 对钢带进行电解镀锌形成条件锌层的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13706177

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2013706177

Country of ref document: EP